接枝量对等离子体接枝聚异丙基丙烯酰胺开关的多孔膜的温度感应透过性的影响

The effect of graft yield on both the thermo-responsive hydraulic permeability and the thermo-respousive diffusional permeability through porous membranes with plasma-grafted poly(N-isopropylacrylamide) (PNIPAM)gates was investigated. Both thermo-respousive flat membranes and core-shell microcapsule membranes with a wide range of graft yield of PNIPAM were prepared using a plasma-graft pore-filling polymerization method. The grafted PNIPAM was formed homogeneously throughout the entire thickness of both the fiat polyethylene membranes andthe microcapsule polyamide membranes. Both the hydraulic permeability and the diffusional permeability were heavily dependent on the PNIPAM graft yield. With increasing the graft yield, the hydraulic permeability (water flux) decreases rapidly at 25℃ because of the decrease of the pore size; however, the water flux at 40℃ increases firstly to a peak because of the increase of hydrophobicity of the pore surface, and then decreases and finally tends to zero because of the pore size becoming smaller and smaller. For the diffusional permeability, the temperature shows different effects on the diffusional permeability coefficients of solutes across the membranes. When the graft yield was low, the diffusional coefficient of solute across the membrane was higher at temperature above the lower critical solution temperature (LCST) than that below the LCST; however, when the graft yield was high, the diffusional coefficient was lower at temperature above the LCST than that below the LCST. It is very important to choose or design a proper graft yield of PNIPAM for obtaining a desired thermo-respousive “on/off“ hydraulic or ditfusional permeability.     

Effect of Graft Yield on the Thermo-Responsive Permeability Through Porous Membranes with Plasma-Grafted Poly(N-isopropylacrylamide)Gates

The effect of graft yield on both the thermo-responsive hydraulic permeability and the thermo-responsive diffusional permeability through porous membranes with plasma-grafted poly(AT-isopropylacrylamide) (PNIPAM) gates was investigated. Both thermo-responsive flat membranes and core-shell microcapsule membranes with a wide range of graft yield of PNIPAM were prepared using a plasma-graft pore-filling polymerization method. The grafted PNIPAM was formed homogeneously throughout the entire thickness of both the flat polyethylene membranes and the microcapsule polyamide membranes. Both the hydraulic permeability and the diffusional permeability were heavily dependent on the PNIPAM graft yield. With increasing the graft yield, the hydraulic permeability (water flux) decreases rapidly at 25℃ because of the decrease of the pore size; however, the water flux at 40℃ increases firstly to a peak because of the increase of hydrophobicity of the pore surface, and then decreases and finally tends to zero because o     

Effect of sol size on nanofiltration performance of a sol-gel derived microporous zirconia membrane

This paper reports the effect of sol size on nanofiltration performances of sol–gel derived microporous zirconia membranes. Microstructure, pure water flux, molecular weight cut-off (MWCO) and salt retention of zirconia membranes derived from zirconia sols with different sizes were characterized. Thermal evolution, phase compo-sition, microstructure and chemical stability of unsupported zirconia membranes (powder) were determined by thermogravimetric and differential thermal analysis, X-ray diffraction, nitrogen adsorption–desorption and static solubility measurements. Results show that nanofiltration performance of zirconia membranes is highly depen-dent on sol size. The sol with an average size of 3.8 nm, which is smaller than the pore size of theγ-Al2O3 support (pore size:5–6 nm), forms a discontinuous zirconia separation layer because of excessive penetration of sol into the support. This zirconia membrane displays a MWCO value towards polyethylene glycol higher than 4000 Da. A smooth and defect-free zirconia membrane with a MWCO value of 1195 Da (pore size:1.75 nm) and relative high retention rates towards MgCl2 (76%) and CaCl2 (64%) was successfully fabricated by dip-coating the sol with an appropriate size of 8.6 nm. Zirconia sol with an average size of 12 nm exhibits colloidal nature and forms a zirconia membrane with a MWCO value of 2332 Da (pore size:2.47 nm). This promising microporous zirconia membrane presents sufficiently high chemical stability in a wide pH range of 1–12.     

Insight into fouling behavior of poly(vinylidene fluoride) (PVDF) hollow fiber membranes caused by dextran with different pore size distributions

Membrane fouling is the key problem that occurs in membrane process for water treatment. However, how membrane microstructure influences the fouling behavior is still not clear. In this study, fouling behavior caused by dextran was deeply and systematically investigated by employing four poly(vinylidene fluoride)(PVDF)membranes with different pore sizes, ranging from 24 to 94 nm. The extent of fouling by dextran was accurately characterized by pore reduction, flux decline, and the change of critical flux. The result shows that membrane with the smallest pore size of 24 nm experienced the smallest fouling rate and the lowest fouling extent. As the membrane pore size increased, the critical flux ranges were 105-114, 63-73, 38-44 and 34-43 L·m~(-2)·h~(-1),respectively. The critical flux and fouling resistances indicated that the fouling propensity increases with the increase of membrane pore size. Two pilot membrane modules with mean pore size of 25 nm and 60 nm were applied in membrane filtration of surface water treatment. The results showed that serious irreversible membrane fouling occurred on the membrane with pore size of 60 nm at the permeate flux of40.5 L·m~(-2)·h~(-1).On the other hand, membrane with pore size of 25 nm exhibited much better anti-fouling performance when permeate flux was set to 40.5,48 and 60 L·m~(-2)·h~(-1).     

混凝耦合多孔陶瓷膜净化河水简

Membrane filtration technology combined with coagulation is widely used to purify river water. In this study, micro filtration （MF） and ultrafiltration （UF） ceramic membranes were combined with coagulation to treat local river water located at Xinghua, Jiangsu province, China. The operation parameters, fouling mechanism and pilot-scale tests were investigated. The results show that the pore size of membrane has small effect on the pseudo-steady flux for dead-end filtration, and the increase of flux in MF process is more than that in UF process for cross-flow filtration with the same increase of cross-flow velocity. The membrane pore size has little influence on the water quality. The analysis on membrane fouling mechanism shows that the cake filtrationhas significant in fluence on the pseudo-steady flux and water quality for the membrane with pore size of 50, 200 and 500 nm. For the membrane with pore size of 200 nm and backwashing employed in our pilot study, a constant flux of 150 L-m^-2-h^-1 was reached during stable operation, with the removal efficiency of turbidity, total organic carbon （TOC） and UV254 higher than 99%, 45% and 48%, respectively. The study demonstrates that coagulation-porous ceramic membrane hybrid process is a reliable method for river water purification.     

Fabrication of poly(vinylidene fluoride) membrane via thermally induced phase separation using ionic liquid as green diluent

Ionic liquid(IL), 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM]PF6) as a new and environmentally friendly diluent was introduced to prepare poly(vinylidene fluoride)(PVDF) membranes via thermally induced phase separation(TIPS). Phase diagram of PVDF/[BMIM]PF6 was measured. The effects of polymer concentration and quenching temperature on the morphologies, properties, and performances of the PVDF membranes were investigated. When the polymer concentration was 15 wt%, the pure water flux of the fabricated membrane was up to nearly 2000 L·m~(-2)·h~(-1), along with adequate mechanical strength. With the increasing of PVDF concentration and quenching temperature, mean pore size and water permeability of the membrane decreased. SEM results showed that PVDF membranes manufactured by ionic liquid(BMIm PF6) presented spherulite structure. And the PVDF membranes were represented as β phase by XRD and FTIR characterization. It provides a new way to prepare PVDF membranes with piezoelectric properties.     

Modeling of the Relationship Between Pore Size Distribution and Thickness of Ceramic MF Membrane

The pore size distribution(PSD)measured by the gas bubble point(GBP)method ofceramic microfiltration(MF)membranes prepared by suspension technique was found to be signifi-cantly influenced by the membrane thickness.A culm-like model for pore structure was introduced tocharacterize the membrane pores instead of the conventional model which does not reflect the radiusvariation along the pore passages and is unable to explain the thickness effect on the membrane PSD.A laminate structure,taking the culm-like model for pore structure into consideration,was hypoth-esized for ceramic MF membranes.A mathematical model was then established to quantitativelydescribe the relationship between the membrane number PSD and the membrane thickness.Goodresults were obtained for the correlation of mean pore size and simulation of the PSD for ceramicMF membranes.     

硅橡胶复合膜用于渗透蒸发的膜传质动力学(Ⅱ)膜内的扩散传质

The pervaporation of organics from dilute aqueous solution through a novel plate composite silicone rubber membrane was investigated. The measured and derived data indicated that the composite membrane possessed very high permeation flux and stable selectivity for dilute organic aqueous solution. Based upon the well- known resistance-in- series model, diffusive mass transfer behavior in membrane was investigated by calculation from the measured data with different skin layer thickness of membranes. The experimental results showed that the diffusive mass transfer coefficient conformed to Arrhenius correlation with temperature and was independent of the flow status. The diffusivities of the given alcohols in membrane had an order of magnitude 10 m-10·s-1 at a wider range of temperature, which is similar to those reported in literatures.     

添加剂和凝结剂温度对用无溶剂致相位分离法生产高性能PVDF/聚醚F127混合中空光纤膜的影响(英文)

Poly(vinylidene fluoride)(PVDF) has become one of the most popular materials for membrane prepara-tion via nonsolvent induced phase separation(NIPS) process.In this study,an amphiphilic block copolymer,Plu-ronic F127,has been used as both a pore-former and a surface-modifier in the fabrication of PVDF hollow fiber membranes to enhance the membrane permeability and hydrophilicity.The effects of 2nd additive and coagulant temperature on the formation of PVDF/Pluronic F127 membranes have also been investigated.The as-spun hollow fibers were characterized in terms of cross-sectional morphology,pure water permeation(PWP),relative molecular mass cut-off(MWCO),membrane chemistry,and hydrophilicity.It was observed that the addition of Pluronic F127 significantly increased the PWP of as-spun fibers,while the membrane contact angle was reduced.However,the size of macrovoids in the membranes was undesirably large.The addition of a 2nd additive,including lithium chlo-ride(LiCl) and water,or an increase in coagulant temperature was found to effectively suppress the macrovoid for-mation in the Pluronic-containing membranes.In addition,the use of LiCl as a 2nd additive also further enhanced the PWP and hydrophilicity of the membranes,while the surface pore size became smaller.PVDF hollow fiber with a PWP as high as 2530 L?m?2?h?1?MPa?1,a MWCO of 53000 and a contact angle of 71° was successfully fabricated with 3%(by mass) of Pluronic F127 and 3%(by mass) of LiCl at a coagulant temperature of 25 °C,which shows better performance as compared with most of PVDF hollow fiber membranes made by NIPS method.     

硅橡胶复合膜渗透汽化分离硫/汽油混合物

Worldwide environment has resulted in a limit on the sulfur content of gasoline. It is urgent to investigate the desulfurization of gasoline. The polydimethylsiloxane (PDMS)/polyetherimide (PEI) composite membranes were prepared by casting a PDMS solution onto porous PEI substrates and characterized by scanning electron microscope (SEM). The membranes were used for sulfur removal from gasoline by pervaporation. The effects of feed temperature, sulfur content in the feed and PDMS layer thickness on membrane performance were investigated, and an activation energy of permeation was obtained. Experimental results indicated that higher feed temperature yielded higher total flux and lower sulfur enrichment factor. The total flux varied little with the increase of sulfur content in the feed, but the sulfur enrichment factor first increased with the amount of thiophene added into the gasoline, and then the variation was little. The increase of PDMS layer thickness resulted in a smaller flux but a larger sulfur enrichment factor. The result indicates that the PDMS/PEI composite membranes are promising for desulfurization by pervaporation.     

温度感应式开关膜的接枝率对其开关特性的影响

利用等离子体诱导填孔接枝聚合法将聚(N-异丙基丙烯酰胺)（PNIPAM）接枝聚合在聚偏氟乙烯（PVDF）微孔膜上制备了一系列具有较宽接枝率范围的温度感应式开关膜,系统地研究了接枝率对膜的温度感应开关特性的影响.结果表明,开关膜的接枝率对膜的过滤通量、温度感应开关系数和膜孔径感温变化倍数都有十分重要的影响.接枝率在小于等于2.81%时,温度感应开关系数和膜孔径感温变化倍数均随接枝率增加而增加;而对于接枝率大于等于6.38%的膜,膜开关系数和膜孔径感温变化倍数总是趋近于1,膜不具备温度感应开关特性.为了获得预期的开关性能,必须将膜的接枝率控制在适当的范围.     

PH值与温度感应型智能开关膜的研究

利用等离子体诱导填孔接技聚合法将聚异而基丙烯酰胺(PNIPAM)或聚丙烯酸(PAAC)接枝聚合在聚偏氟乙烯(PVDF)微孔膜上,制备了一系列具有较宽接枝率范围的温度感应型开关膜(接枝PNIPAM)和pH值感应型开关膜(接技PAAC),研究了接枝率对膜的温度感应以及pH值感应开关特性的影响。研究结果表明,开关膜的接枝率对膜的开关特性有十分重要的影响。对于温度感应型开关膜,当接枝率等于2.81％时,可以获得最好的膜孔开关特性;而且发现在溶质扩散时,低接枝率膜与高接技率膜呈现两种完全相反的开关特性。对于pH值感应型开关膜,当接枝率为1.01％时膜孔开关特性最好。因此,为了获得预期的开关特性,必须将接枝率控制在合适的范围内。     

Thermo‐Responsive Gating Characteristics of Poly(N‐isopropylacrylamide)‐Grafted Membranes

Both hydrophilic Nylon‐6 membranes and hydrophobic poly(vinylidene fluoride) (PVDF) membranes, with a wide range of grafting yields of poly(N‐isopropylacrylamide) (PNIPAM), were prepared using the plasma‐graft pore‐filling polymerization method. The effect of the physical and chemical properties of the substrates on the thermo‐responsive gating characteristics of the PNIPAM‐grafted membranes was investigated experimentally. For both the PVDF and Nylon‐6 membranes, the grafted PNIPAM polymers were found not only on the membranes outer surface, but also on the inner surfaces of the pores throughout the entire thickness of the membrane. The thermo‐responsive gating characteristics of the PNIPAM‐grafted membranes were heavily affected by the physical and chemical properties of the porous membrane substrates. The PNIPAM‐g‐Nylon‐6 membranes exhibited a much larger thermo‐responsive gating coefficient than the PNIPAM‐g‐PVDF membranes. Furthermore, to achieve the largest thermo‐responsive gating coefficient, the corresponding optimum grafting yield of PNIPAM for the PNIPAM‐g‐Nylon‐6 membranes was also larger than that for the PNIPAM‐g‐PVDF membranes.     

多孔膜基材对等离子体接枝膜微观结构的影响

采用等离子体诱导接枝聚合法,在有机聚偏氟乙烯(PVDF)膜、尼龙(N6)膜和无机多孔阳极氧化铝(PAA)膜上接枝甲基丙烯酸(MAA),系统地研究了多孔膜基材及接枝工艺条件对接枝开关膜微观结构的影响。结果发现,对于PVDF基材膜,单体溶液脱气次数越多接枝率越大。对于不同类别的多孔膜基材,采用相同工艺条件接枝时,N6膜的接枝率高于PVDF膜,PAA膜接枝率最低。在接枝率相近的时候,接枝层在PVDF膜整个断面孔内和表面均存在,而N6膜则主要集中在表层。在PAA膜上接枝时发现,等离子体照射功率的强弱对基材膜的影响很大,当功率超过50W时,PAA膜表层就会被刻蚀而导致膜的质量减轻。     

聚N-异丙基丙烯酰胺接枝核孔膜微观结构及温敏响应特性

采用等离子体诱导填孔接枝聚合法在聚碳酸酯核孔（PCTE）膜上成功地接枝了聚N-异丙基丙烯酰胺（PNIPAM）,采用X射线光电子能谱（XPS）、傅里叶变换红外光谱仪（FT-IR）、扫描电镜（SEM）、原子力显微镜（AFM）、接触角测量仪和水通量实验,系统地研究了PNIPAM-g-PCTE膜的化学成分、微观结构和温敏特性,以期为环境感应型开关膜的设计和制备提供指导.结果表明,PNIPAM被均匀地接枝在PCTE膜表面和膜孔中;当填孔率F<44.2%时,PNIPAM-g-PCTE膜的膜孔由于孔内接枝物的体积变化而表现出温敏开关特性,并且膜孔径随着F的增大而减小;当F>44.2%以后,水溶液中膜的膜孔被溶胀的PNIPAM接枝链堵塞,此时PNIPAM-g-PCTE膜不再具有温度开关特性;40 ℃时膜孔被完全堵塞的临界填孔率范围在30%～40%之间;随着温度从25 ℃增加到40 ℃,PNIPAM-g-PCTE膜表面的接触角也从58.5°增加到87.9°;PNIPAM-g-PCTE膜水通量的温敏开关特性主要取决于膜孔径的变化,而不是膜表面亲水性的改变.     

智能膜开关尺寸与孔径的匹配性对膜响应性能的影响规律

智能膜的响应性能是其主要性能之一。本文借助计算流体力学（CFD）模拟,以孔壁排布有聚N-异丙基丙烯酰胺（PNIPAM）智能微球的单直膜孔为模型,定量系统地考察了智能微球的响应倍数以及微球尺寸与膜孔径的匹配性对膜温度响应性能的影响规律,并通过实验验证了模拟结果的可靠性。CFD模拟结果表明,当智能开关与膜孔径的相对比值一定时,温度响应开关系数随着微球响应倍数的减小而逐渐增大。当相对比值小于0.4时,实测的温度响应开关系数与固载量100%的模拟结果相吻合;而当相对比值大于0.4时,其与固载量为67%的模拟结果相吻合。通常当相对比值在0.4～0.65之间时,智能膜可以同时获得良好的温度响应性能和稳定的渗透性能。该研究结果可望为设计和制备高性能智能膜提供理论指导和实验基础。     

Gating Characteristics of Thermo‐Responsive Membranes with Grafted Linear and Crosslinked Poly(N‐isopropylacrylamide) Gates

Thermo‐responsive porous membranes with grafted linear and crosslinked poly(N‐isopropylacrylamide) (PNIPAM) gates are successfully prepared at temperatures above and below the lower critical solution temperature (LCST) of PNIPAM by using a plasma‐induced grafting polymerization method, and the effects of operation pressure and grafting temperature on the thermo‐responsive gating characteristics of the prepared membranes are investigated systematically. The fluxes of water through the grafted membranes increase simply with increasing the operation pressure no matter whether the environmental temperature is 40 °C or 25 °C. Under high operation pressure (e.g., higher than 0.14 MPa), the grafted linear PNIPAM gates deform to a certain extent, whereas the grafted crosslinked PNIPAM gates do not deform. For both membranes with grafted linear and crosslinked PNIPAM gates, the membranes prepared at 25 °C (below the LCST of PNIPAM) show larger thermo‐responsive gating coefficients than those prepared at 40 °C (above the LCST of PNIPAM), which results from different distributions of grafted PNIPAM gates in the membrane pores. When the PNIPAM gates are grafted at 25 °C, the grafted layer near the membrane surface is much thicker than that inside the membrane pores; on the other hand, when the PNIPAM gates are grafted at 40 °C, the grafted layer is homogeneously formed throughout the whole pore length. Both linear and crosslinked grafted PNIPAM gates in the membrane pores exhibit stable and repeatable thermo‐responsive “open‐close” switch performances under the operation pressure of 0.26 MPa. The results in this study provide valuable guidance for designing, fabricating, and operating thermo‐responsive gating membranes with desirable performances.     

Influence of polydopamine deposition conditions on pure water flux and foulant adhesion resistance of reverse osmosis, ultrafiltration, and microfiltration membranes

The influence of polydopamine (PDOPA) deposition and poly(ethylene glycol) (PEG) grafting on pure water flux and bovine serum albumin (BSA) adhesion of two polysulfone ultrafiltration (UF) membranes, a poly(vinylidene fluoride) microfiltration (MF) membrane, and a polyamide reverse osmosis (RO) membrane is reported. When modified with PDOPA, all membranes exhibited a systematic reduction in protein adhesion. For example, 90 min of PDOPA deposition led to at least 96% reduction in BSA adhesion to these membranes at neutral pH. BSA adhesion was further reduced by subsequent PEG grafting to PDOPA (PDOPA-g-PEG). The membranes’ pure water flux values (i.e., with no foulants present) were influenced to different extents by PDOPA and PDOPA-g-PEG modifications. In the porous membranes (i.e., the UF and MF membranes), the pure water flux reduction due to these modifications correlated with membrane pore size, with the smallest flux reductions observed in the MF membrane (e.g., <1% flux reduction for all PDOPA modification times considered), which have the largest pores, and the largest flux reductions occurring in UF membranes (e.g., a 40% flux reduction after 90 min of PDOPA deposition), which have pore sizes on the order of the PDOPA deposition thickness. The RO membranes, which are essentially non-porous, exhibited a flux reduction of 25% after 90 min of PDOPA deposition.     

pH或/和温度双重响应嵌段接枝膜的开关特性

利用原子转移自由基聚合法(ATRP)成功地制备了聚甲基丙烯酸-嵌段-聚N-异丙基丙烯酰胺(PMN)和聚N-异丙基丙烯酰胺-嵌段-聚甲基丙烯酸(PNM)接枝开关膜。通过通量实验系统考察了两类开关膜分别或同时对pH和温度的响应性。结果表明:用ATRP法接枝嵌段共聚物开关中第一段接枝物的接枝率总是高于第二段接枝物的接枝率;该嵌段接枝开关膜对pH和温度同时响应的开关系数要大于其对单一pH或温度响应的开关系数;嵌段接枝开关中第一段接枝物对膜孔的"开"或"关"起主导作用,而第二段接枝物的影响相对较小。实验结果还表明,PMAA的pH响应开关系数比PNIPAM的温度响应开关系数显著。研究结果为设计和制备双重或多重嵌段接枝开关膜提供了有价值的参考。     

Pilot-scale spiral wound membrane assessment for THM precursor rejection from upland waters

The outcomes of a pilot-scale study of the rejection of trihalomethanes (THMs) precursors by commercial ultrafiltration/nanofiltration (UF/NF) spiral-wound membrane elements are presented based on a single surface water source in Scotland. The study revealed the expected trend of increased flux and permeability with increasing pore size for the UF membranes; the NF membranes provided similar fluxes despite the lower nominal pore size. The dissolved organic carbon (DOC) passage decreased with decreasing molecular weight cut-off, with a less than one-third the passage recorded for the NF membranes than for the UF ones.

The yield (weight % total THMs per DOC) varied between 2.5% and 8% across all membranes tested, in reasonable agreement with the literature, with the aromatic polyamide membrane providing both the lowest yield and lowest DOC passage. The proportion of the hydrophobic (HPO) fraction removed was found to increase with decreasing membrane selectivity (increasing pore size), and THM generation correlated closely (R² = 0.98) with the permeate HPO fractional concentration.